Perfume blend including 2-keto-6-substituted-dioxanes-(1,4)

ABSTRACT

Novel 2-keto-6-substituted dioxane-(1,4) compounds having the structural formula: ##EQU1## wherein R is an alkyl radical having 6-9 carbon atoms, mixtures thereof, and R&#39;OCH 2  wherein R&#39; is an alkyl radical having 5-8 carbon atoms. The novel compounds exhibit desirable fragrance and flavor properties.

This is a division of application Ser. No. 452,229 filed Mar. 18, 1974now abandoned.

BACKGROUND OF THE INVENTION

There is a continuing search for materials having desirable fragranceproperties. Such materials are sought either to replace costly naturalmaterials or to provide new fragrance or perfume types which have notheretofore been available. Especially desirable qualities for substanceshaving interesting fragrances are stability in a wide variety ofperfumed articles and perfume compositions, ease of manufacture andintensity of aroma.

The Prior Art

Insofar as applicants are aware, the 2-keto-6-alkyl and6-(alkyloxymethyl)-dioxane-(1,4) disclosed and claimed in the instantapplication have not heretofore been known.

U.S. Pat. No. 3,280,065 relates to the preservation of latexes byincorporating 2-keto-6-methyl-dioxane-(1,4) and2-keto-3-methyl-6-ethyl-dioxane-(1,4) into the latex to produce a latexcomposition stabilized against biological attack.

The Invention

The present invention relates to novel compounds which possess desirableodorous qualities and perfume-containing compositions containing thesenovel compounds as olfactory agents.

More particularly, the present invention provides novel 2-keto-6-alkyland 6-substituted-dioxane (1,4) compounds of the formula: ##EQU2##wherein R is an alkyl group of from C₆ to C₉, mixtures thereof andR'OCH₂ --wherein R' is an alkyl group of from 5-8 carbon atoms. It hasbeen discovered that these compounds possess desirable fragranceproperties and are useful in perfume compositions. Typical of thecompounds encompassed by the present invention are2-keto-6-hexyl-dioxane-(1,4), 2-keto-6-heptyl-dioxane-(1,4),2-keto-6-octyl-dioxane-(1,4), 2-keto-6-nonyl-dioxane-(1,4), 2-keto-6-(C₇-C₈ alkyl-dioxane)-(1,4), 2-keto-6-(C₇ -C₉ alkyl)-dioxane-(1,4),2-keto-6-(pentyloxymethyl)-dioxane-(1,4),2-keto-6-(hexykloxymetyl)-dioxane-(1,4),2-keto-6-(heptyloxylmethyl)-dioxane-(1,4),2-keto-6-(octyloxymetyl)-dioxane-(1,4 ).

The 2-keto-6-substituted-dioxane-(1,4) compounds of this invention areolfactory agents and can be incorporated into a wide variety ofcompositions. The compounds can be added to perfume compositions in itspure form or it can be added to mixtures of materials infragrance-imparting compositions to provide a desired fragrancecharacter to a finished perfume material. The perfume and fragrancecompositions obtained according to this invention are suitable in a widevariety of perfumed articles and can also be used to enhance, modify orreinforce natural fragrance materials.

The term "perfume composition" is used herein to mean a mixture ofcompounds including, for example, natural oils, synthetic oils,alcohols, aldehydes, ketones, esters, lactones, and frequentlyhydrocarbons which are admixed so that the combined odors of theindividual components produce a pleasant or desired fragrance. Suchperfume compositions or the novel compounds of this invention can beused in conjunction with carriers, vehicles, solvents, dispersants,emulsifiers, surface-active agents, aerosol propellants and the like.

In perfume compositions the individual components contribute theirparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum effect of each ingredient. Thus, the2-keto-6-substituted dioxane-(1,4) compounds of this invention can beused to alter the aroma characteristics of a perfume composition, forexample, by high lighting or moderating the olfactory reactioncontributed by another ingredient of the composition.

The amount of 2-keto-6-substituted-dioxane-(1,4) compound of thisinvention which will be effective in perfume compositions depends onmany factors including the other ingredients, their amounts and theeffects which are desired. It has been found that perfume compositionscontaining as little as 0.01 to 2% by weight of mixtures or compounds ofthis invention, or even less can be used to impart a pleasant odor tosoaps, cosmetics and other products. The amount employed will depend onconsiderations of cost, nature of end product, the effect desired in thefinished product, and the particular fragrance sought.

The keto-6-substituted-dioxane-(1,4) compounds disclosed herein can beused alone in fragrance-modifying composition, or in a perfumecomposition as an olfactory component in detergents and soaps; spacedeodorants; perfumes; colognes; bath preparations such as bath oil, bathsalts; hair preparations such as lacquers; brilliantives, pomades, andshampoos; cosmetic preparations such as creams, deodorants, handlotions, sun screens; powders such as talcs, dusting powders, facepowder and the like. When the compound of this invention are used inperfumed articles such as the foregoing, it can be used in amounts of0.1% or lower. Generally, it is preferred not to use more than about2.0% in the finished perfumed article, since the use of too much willtend to unbalance the total aroma and will needlessly raise the cost ofthe article.

The novel 2-keto-6-alkyl-dioxane-(1,4) compounds of the presentinvention can be prepared by reacting an alkali metal alcoholate of a1,2-alkanediol with a monohalogenated acetic acid to form theintermediate compound, alkali metal carboxymethyl-2-hydroxyalkyl ether.The 2-keto-6-alkyl-dioxane-(1,4) is obtained from the intermediatealkali metal carboxymethyl-2-hydroxyalkyl ether by cyclizing underacidic conditions.

The 1,2-alkanediol reactants useful for the preparation of the novelcompounds of the present invention can be any 1,2-diol having thestructure: ##EQU3## wherein R is an alkyl radical having 6-9 carbonatoms and mixtures thereof. Illustrative examples of the 1,2-alkanediolreactant include 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, and1,2-undecanediol. The alkali metal alcoholate of the 1,2-alkanediols areprepared by action of alkali metal hydroxides, for example, sodiumhydroxide and potassium hydroxide on the diol. The 1,2-alkanediols canbe prepared by known methods. In one known technique, 1,2-alkanediolsare prepared from the corresponding 1-alkene oxide or alpha-olefinepoxides by treating the oxide with water containing a catalytic amountof mineral acid.

Any monohalogenated acetic acid may be employed as the reactant, butchloroacetic acid and bromoacetic acid are preferred, particularly theformer.

The alkali metal alcoholate of 1,2-alkanediol is prepared in situ byadding powdered alkali metal hydroxide, for example, sodium hydroxide orpotassium hydroxide, to 1,2-alkanediol. Approximately 2 moles of alkalimetal hydroxide is employed per mole of alkanediol. The addition of thealkali metal hydroxide to the diol is carried out with vigorousstirring. The compounds react very easily and the reaction is conductedat room temperature or at slightly elevated temperature, for example,40°-50°C.

Reaction of the monohalogenated acetic acid with the alkali metalalcoholate of the 1,2-alkanediol is carried out by slowly adding theacetic acid reagent to the alcoholate diol. The addition is conducted ata slightly elevated temperature, for example, 50°-60°C and the reactionis maintained at this temperature until completion. Approximatelyequimolar proportions of the reactants is employed for this reaction.The reaction product is the alkali metal carboxymethyl 2-hydroxyalkylether. This compound is extracted from the reaction mixture with asuitable solvent, for example pet ether, ethyl ether, ethyl acetate,benzene. The desired product, 2-keto-6-alkyl-dioxane-(1,4), is preparedfrom the above-mentioned ether compound by cyclizing with a mineral acidsuch as hydrochloric acid, sulfuric acid, phosphoric acid. The finalproduct is isolated by distillation under reduced pressure.

The novel 2-keto-6-(alkyloxymethyl)-dioxane-(1,4) compounds of thepresent invention can be prepared by reacting an alkali metal alcoholateof a glycerol monoalkyl ether with a monohalogenated acetic acid.

The glycerol monoalkyl ethers that can be employed in preparing thenovel compounds of this invention have the structure: ##EQU4## whereinR' is an alkyl radical having 5-8 carbon atoms. Illustrative examples ofthe monoalkyl ether glycerols include glycerol monopentyl ether,glycerol monohexyl ether, glycerol monoheptyl ether, and the monooctylether of glycerol. The glycerol ethers can be prepared by methods wellknown in the art. One method employs the addition of the appropriatealcohol to epichlorohydrin. The reaction is catalyzed by stannouschloride. The epichlorohydrin is slowly added to the alcohol at anelevated temperature, for example, 80°-90°C and maintained at thetemperature for about 1 hour. Cool the reaction mixture to roomtemperature or below and add an equimolar amount of sodium hydroxide toconvert the chlorohydrin to the corresponding epoxide. The reactionmixture is heated to reflux after adding water, sulfuric acid, andsufficient acetone to form a homogeneous solution. After neutralizingthe reaction mixture the glycerol monoalkyl ether is isolated byextracting with pet ether and distilling the product under reducedpressure.

The method for preparing 2-keto-6(alkyloxymethyl-dioxane-(1,4) from thealkali metal alcoholate of glycerol monoalkyl ether and amonohalogenated acetic acid is the same as described above for the2-keto-6-alkyl-dioxane-(1,4) compounds.

The 2-keto-6-substituted-dioxane-(1,4) compound of the present inventionfind particular utility in detergent compositions. The dioxanes may ifdesired be employed as the sole perfume ingredient, but normally will beused as component of a blend of perfume oils to impart a desirablemodification to the blend. The novel dioxanes are stable toward all ofthe substances customarily employed in neutral or acidic detergentcompositions.

The detergent compositions wherein the2-keto-6-substituted-dioxanes-(1,4) are useful may comprise anysurfactant species, whether anionic, cationic, nonionic, or amphoteric,including the soaps. All of the usual builder substances may beemployed, such as the polyphosphates, orthophosphates, carbonates,citrates, oxydiacetates, oxydisuccinates, carboxymethyloxysuccinates,etc. Oxidizing agents, such as the perborates, hypochlorites,dichlorocyanurates, etc. have no effect on the odor of the2-keto-6-substituted-dioxane-(1,4) compounds when employed together indetergent or dry bleach compositions.

When employed in admixture with other perfume components, the proportionof 2-keto-6-substituted-dioxane-(1,4) may range from about 1 to about99%, on the mixture basis. A preferred range is about 10 to about 90%,and most generally a mixture will contain about 20 to about 75% of thedioxane compound by weight.

When a perfume blend containing one or more2-keto-6-substituted-dioxanes-(1,4) in the useful proportions set forthherein is employed in a detergent or soap composition, the proportion of2-keto-6-substituted-dioxanes-(1,4) in the total composition willusually vary from about 0.001 to about 2%, by weight.

The selection of any particular component or proportion thereof of adetergent or soap composition wherein a 2-keto-6-substituted-dioxane-(1,4) is to be incorporated will depend upon the detergency effectdesired, and forms no part of the present invention.

Suitable detergent or soap compositions may be in any of the usualforms, particulate, liquid, bar, or briquette. Shampoo compositions aresuitable, and may be based on soaps or nonsoap detergents.

Suitable soap and nonsoap detergent species, builders to enhancedetergency, and miscellaneous adjuvants are discussed in the texts,"Surface Active Agents" by Schwartz and Perry, and "Surface ActiveAgents and Detergents" by Schwartz, Perry and Berch, both IntersciencePublishers, New York, N. Y., the disclosures of both being incorporatedherein by reference.

Suitable particulate detergent compositions are disclosed in U.S. Pat.Nos. 2,829,102, 2,829,108 and 3,188,291, paticulate soap compositions inU.S. Pat. Nos. 2,329,694 and 2,940,935, detergent tablets in U.S. Pat.Nos. 3,055,837, 3,043,779 and 2,894,912, soap tablets in U.S. Pat. Nos.2,404,298, 2,649,417, 2,215,539 and 3,284,363, liquid detergentcompositions in U.S. Pat. Nos. 2,941,950 and 3,052,635 and shampoos inU.S. Pat. Nos. 3,086,943 and 3,263,733, all of which are incorporatedherein by reference.

EXAMPLE 1 Preparation of 2-keto-6-hexyl-dioxane-(1,4)

A homogeneous clear solution is prepared by adding 3 moles of acetone to1 mole of octene (1,2) oxide at room temperature. After adding 50 gramsof 5% aqueous sulfuric acid to the solution, the acetone is evaporatedoff and the resulting solution is neutralized by adding an aqueoussodium hydroxide. The neutralized solution is extracted with pet etherand the extract dried over anhydrous magnesium sulfate. The pet ether isstripped off and 1,2-octanediol is obtained by distilling under vacuo,b.p. 103°-105°C/0.2 mm.

Two moles of powdered sodium hydroxide is added to 1 mole (146g) of1,2-octanediol with vigorous stirring at room temperature. During theaddition of the base, the temperature of the reaction mixture increasesfrom room temperature to about 40°-50°C and the reaction mixture becomesa thick pasty mass. One mole of monochloroacetic acid is slowly added tothe reaction mixture while the temperature is maintained between50°-55°C. The reaction mixture is then stirred for 1.5 hours at50°-60°C. After cooling to room temperature, the reaction mixture isextracted with pet ether; the extracts are acifified with concentratedhydrochloric acid and then dried over anhydrous magnesium sulfate. Thepet ether is removed and 2-keto-6-hexyl-dioxane-(1,4) is distilled atreduced temperature, b.p. 90°-111°C/0.2 mm.

The novel 2-keto-6-hexyl-dioxane-(1,4) compound has an aldehydic, woodand wholesome odor.

The infra red spectrum of 2-keto-6-hexyl-dioxane-(1,4) exhibited thefollowing peaks:

    5.75     μ    1750    cm.sup.-.sup.1                                                                         (strong)                                    7.05     μ    1420    cm.sup.-.sup.1                                                                         (weak)                                      7.45     μ    1340    cm.sup.-.sup.1                                                                         (moderate)                                  9.1      μ    1110    cm.sup.-.sup.1                                                                         (strong)                                    10.7     μ    935     cm.sup.-.sup.1                                                                         (strong)                                    8.0      μ    1250    cm.sup.-.sup.1                                                                         (strong)                                    8.25     μ    1215    cm.sup.-.sup.1                                                                         (strong)                                

EXAMPLE 2 Preparation of 2-keto-6-octyl-dioxane-(1,4)

A homogeneous clear solution is prepared by adding 3 moles of acetone to1 mole of 1-decene oxide at room temperature. After adding 50 grams of5% aqueous sulfuric acid to the solution, the acetone is evaporated offand the resulting solution is neutralized by adding an aqueous sodiumhydroxide. The neutralized solution is extracted with pet ether and theextract dried over anhydrous magnesium sulfate. The pet ether isstripped off and 1,2-decanediol is obtained by distilling under vacuo.

Two moles of powdered sodium hydroxide is added to 1 mole (174g) of1,2-decanediol with vigorous stirring at room temperature. During theaddition of the base, the temperature of the reaction mixture increasesfrom room temperature to about 40°-50°C and the reaction mixture becomesa thick pasty mass. One mole of monochloroacetic acid is slowly added tothe reaction mixture while the temperature is maintained between50°-55°C. The reaction mixture is then stirred for 1.5 hours at50°-60°C. After cooling to room temperature, the reaction mixture isextracted with pet ether; the extracts are acidified with concentratedhydrochloric acid and then dried over anhyerous magnesium sulfate. Thepet ether is removed and 2-keto-6-octyl-dioxane-(1,4) is distilled atreduced temperature, b.p. 150°C/2.4 mm. The compound exhibited a peachylactone aroma.

EXAMPLE 3 Preparation of 2-keto-6-C₇ -C₈ alkyl-dioxane-(1,4)

A homogeneous clear solution is prepared by adding 3 moles of acetone to1 mole of a mixture of 1-nonene oxide and 1-decene oxide at roomtemperature. After 50 grams of 5% aqueous sulfuric acid to the solution,the acetone is evaporated off and the resulting solution is neutralizedby adding an aqueous sodium hydroxide. The neutralized solution isextracted with pet ether and the extract dried over anhydrous magnesiumsulfate. The pet ether is stripped off and a mixture of 1,2-nonanedioland 1,2-decanediol is obtained by distilling under vacuo.

Two moles of powdered sodium hydroxide is added to 1 mole of a mixtureof 1,2-nonanediol and 1,2-decanediol with vigorous stirring at roomtemperature. During the addition of the base, the temperature of thereaction mixture increases from room temperature to about 40°-50°C andthe reaction mixture becomes a thick pasty mass. One mole ofmonochloroacetic acid is slowly added to the reaction mixture while thetemperature is maintained between 50°-55°C. The reaction mixture is thenstirred from 1.5 hours at 50°-60°C. After cooling to room temperature,the reaction mixture is extracted with pet ether; the extracts areacidified with concentrated hydrochloric acid and then dried overanhydrous magnesium sulfate. The pet ether is removed and 2-keto-6-C₇-C₈ alkyl dioxane-(1,4) is distilled at reduced temperature, b.p.123°-150°C/0.2-0.9 mm. This compound exhibits an aroma described as"aldehydic with an oily background note."

EXAMPLE 4 Preparation of 2-keto-6-C₇ -C₉ -dioxane-(1,4)

A homogeneous clear solution is prepared by adding 3 moles of acetone toa (1:1:1) mixture of 1-nonene oxide, 1-decene oxide, and 1-undeceneoxide at room temperature. After adding 50 grams of 5% aqueous sulfuricacid to the solution, the acetone is evaporated off and the resultingsolution is neutralized by adding an aqueous sodium hydroxide. Theneutralized solution is extracted with pet ether and the extract driedover anhydrous magnesium sulfate. The pet ether is stripped off and amixture of 1,2-nonanediol, 1,2-decanediol and 1,2 undecanediol isobtained by distilling under vacuo.

Two moles of powdered sodium hydroxide is added to 1 mole of a mixtureof 1,2-nonanediol, 1,2-decanediol and 1,2-undecanediol with vigorousstirring at room temperature. During the addition of the base, thetemperature of the reaction mixture increases from room temperature toabout 40°-50°C and the reaction mixture becomes a thick pasty mass. Onemole of monochloroacetic acid is slowly added to the reaction mixturewhile the temperature is maintained between 50°-55°C. The reactionmixture is then stirred for 1.5 hours at 50°-60°C. After cooling to roomtemperature, the reaction mixture is extracted with pet ether; theextracts are acifified with concentrated hydrochloric acid and thendried over anhydrous magnesium sulfate. The pet ether is removed and2-keto-6-C₇ -C₉ -dioxane-(1,4) is distilled at reduced temperature.

The novel compound possesses a "peachy" and fresh "odor."

EXAMPLE 5 Preparation of 2-keto-6-(octyloxymethyl)-dioxane-(1,4)

One mole (92.5g) of epichlorohydrin is added over 1 hour to 1 mole(132g) 1-octanol containing a catalytic amount of stannous chloride. Theaddition is carried out at a temperature of about 90°C, and after theaddition is completed the reaction mixture is maintained at 90°C forabout 1 hour. The reaction is allowed to cool to room temperature; about3 moles of water are added and sulfuric acid is then added to thereaction. Sufficient acetone is added to form a homogeneous solution andthen the reaction is heated at reflux for about 1 hour. Cool thereaction mixture to room temperature or below and add an equimolaramount of sodium hydroxide to convert the chlorohydrin to thecorresponding epoxide. The acetone is then evaporated off and theresulting mixture is neutralized with aqueous sodium hydroxide. Theneutralized solution is extracted with pet ether and the extract isdried over anhydrous magnesium sulfate. The pet ether is removed and themonooctylether of glycerol is obtained by distilling under vacuo.

Two moles of powdered sodium hydroxide is added to 1 mole ofmonooctylether of glycerol with vigorous stirring at room temperature.During the addition of the base, the temperature of the reaction mixtureincreases from room temperature at about 40°-50°C and the reactionmixture becomes a thick pasty mass. One mole of monochloroacetic acid isslowly added to the reaction mixture while the temperature is maintainedbetween 50°-55°C. The reaction mixture is then stirred for 1.5 hours at50°-60°C. After cooling to room temperature, the reaction mixture isextracted with pet ether; the extracts are acidified with concentratedhydrochloric acid and then dried over anhydrous magnesium sulfate. Thepet ether is removed and 2-keto-6-(octyloxymethyl)-dioxane-(1,4) isdistilled at reduced temperature.

The following compounds are prepared according to the procedure above:

2-keto-6-(pentyloxymethyl)dioxane-(1,4)

2-keto-6-(hexyloxymethyl)dioxane-(1,4)

2-keto-6-(heptyloxymethyl)dioxane-(1,4)

by employing amyl alcohol, 1-hexanol, and 1-heptanol, respectively inplace of 1-octanol.

Each of the above compounds exhibited a typical lactone aroma.

The foregoing description of the present invention has been presenteddescribing certain operable and preferred embodiments. It is notintended that the invention should be so limited, since variations andmodifications thereof will be obvious to those skilled in the art, allof which are within the spirit and scope of this invention.

What is claimd is:
 1. A perfume blend including an olfactorily effectiveamount of a compound having the formula: ##EQU5## wherein R is R'OCH₂ --wherein R' is an alkyl radical of from C₅ -C₈.
 2. The perfume blend ofclaim 1 wherein R' is C₅.
 3. The perfume blend of claim 1 wherein R' isC₆.
 4. The perfume blend of claim 1 wherein R' is C₇.
 5. The perfumeblend of claim 1 wherein R' is C₈.